Fiber-reactive disazodyestuffs containing a pyrimidine radical

ABSTRACT

DISAZO DYESTUFFS OF THE FORMULA   3-(M(+)(-)O3S-),4-((2-(HO-),6,8-DI(M(+)(-)O3S-)NAPHTHYL)   -N=N-),4&#39;&#39;-((2-X,4-(A-NH-),5-Y-PHENYL)-N=N-)BIPHENYL   WHEREIN A REPRESENTS A FIBER-REACTIVE ACYL RADICAL CAPABLE OF FORMING AT LEAST ONE COVALENT BOND WITH A CELLULOSIC OR POLYAMIDE SUBSTRATE, AND WHEREIN X REPRESENTS HYDROGEN OR LOWER ALKYL AND Y REPRESENTS HYDROGEN, LOWER ALKYL OR LOWER ALKOXY, ARE DISCLOSED AS USEFUL FOR THE DYEING OF THE AFORESAID FIBER MATERIALS, AFFORDING DYEINGS OF GOOD WET-FASTNESS PROPERITIES.

United States Patent 5 6 Int. Cl. C07c 107 /00; C09b 35/20, 43/12 vs.Cl. 260-154 Claims ABSTRACT OF THE 1 DISCLOSURE Disazo dyestulfs of theformula SO3'M+ Y I I l wherein A represents a fiber-reactive acylradical capable of forming at least one covalent bond with a cellulosicor polyamide substrate, and wherein. X represents hydrogen or loweralkyl and Y represents hydrogen, lower alkyl or lower alkoxy, aredisclosed as useful for the dyeing of the aforesaid fiber materials,affording dyeings of good wet-fastness properties.

is reacted with an acylating agent the acyl radical A of which can enterinto at least one covalent bond with the substrate, particularly,natural and regenerated cellulose fibers to form a fiber-reactive disazodyestuff of the general Formula II 3,642,766 Patented Feb. 15, 1972 'icein which formulas M+ represents a colorless cation, especially hydrogenor an alkali metal ion,

A represents a fiber-reactive acyl radical capable of forming at leaston covalent bond with a cellulosic or polyamide substrate, and whichradical does not substantially affect the shade of the remainder of thedyestuit molecule,

X represents hydrogen or a lower alkyl group and Y represents hydrogen,a lower alkyl or a lower alkoxy group.

If X and/or Y represent a lower alkyl group then this is, e.g. themethyl, ethyl, propyl or isopropyl group. If Y is a lower alkoxy groupthis is principally the methoxy or ethoxy group. Preferably, X and Yindependently of each other represents the methyl group or hydrogen.

Suitable as fiber-reactive acyl radical A in the dyestuffs according tothe invention are, for example: the radical of an acid containing atleast one mobile halogen atom and/or a carbon-to-carbon polybond towhich addition can be made, e.g. the radical of chloroacetic orbromoacetic acid, fl-chloropropionic and ,Bbromopropionic acid,propiolic acid, acrylic acid, methacrylic acid, a-chloro,fl chloro-,wbromoand fi-bromo acrylic acid, a,fiand 5,8- dichloroacrylic acid or01,}9- and [3,[3-dibromoacrylic acid, trichloroor tribromo-acrylic acid,crotonic acid, aor fl-chlorocrotonic acid or aor p-bromocrotonic acid,11,,8- dichlorocrotonic acid, maleic acid, monochloroandmonobromo-maleic acid, dichloroand dibromo-maleic acid, fumaric acid,monochloroand monobromo-fumaric acid, dichloroand di'bromo-fumaric acid,fumaric acid monoester, dichloroand dibromo-succinic acid, [3-sulfatoorfi-halogenoethyl-sulfonic acid; the radical of a nitrohalogen benzoicacid or nitrohalogen benzene sulfonic acid having a mobile halogen atom,in particular having fluorine or chlorine in 0- or p-position to thenitro group such as the radical of 3-nitro-4-fluorobenzoic acid or3-nitro- 4-chloro-benzene sulfonic acid; also the radical of apolyhalide of a cyclic imide of carbonic acid, particularly a triazinylor diazinyl radical having at least one mobile halogen atom, e.g. theradical of cyanuric chloride, cyanuric bromide or primary condensationproducts thereof in which a halogen atom is replaced by the optionallyfurther substituted radical of a primary or secondary aliphatic,alicyclic, aromatic or heterocyclic amine, in particular by aniline orits alkyl and sultonic acid or carboxylic acid derivatives, by lowermonoand di-alkylamines as Well as by ammonia, or by the radical of analiphatic, alicyclic, aromaticor heterocyclic hydroxy or thiol compound.Further, A represents a polyhalogenopyrimidine radical such as the diortrichloropyrimidyl, dior trifiuoropyrimidyl or dior tribromopyrimidylradical which, in the 5-position, can have the following substituents,e.g. methyl, ethyl, carboxylic or sulfonic acid amide optionallysubstituted at the nitrogen atom, carboxylic acid methyl or ethyl ester,acyl, e.g. benzoyl, alkylene, e.g. allyl, chlorovinyl, substitutedalkyl, e.g. carboxymethyl, chloromethyl or bromomethyl, particularlyhowever, halogen, the radical of a reactive heterocyclic carboxylic orsulfonic acid such as the radical of halogenopyrimidine carboxylic acid,of 2,3-dihalogenoquinoxaline carboxylic acid or2,3-dihalogenoquinoxaline sulfonic acid, of 2-halogenbenz0-thiaz0le or-oxazole carboxylic or sulfonic acid, of halogenophthalazine carboxylicacid, or halogenoquinazoline carboxylic acid or the radical ofhalogen-6-pyridazon-l-yl-alkylene or halogen-G-pyridazonl-yl-phenylenecarboxylic acid. The radicals of the following compounds areparticularly suitable: 2,4,6-trichloro-, 2,4,6-trifluoroor2,4,6-tribrorno pyrimidine, 2,4,6- trichloro-S-bromopyrimidine,2,4,5,6-tetrachloroor 2,4,5, G-tetrabromo-pyrimidine,2,4-dichloropyrimidine-5- or -6- carboxylic acid,2,3-dichloroquinoxaline-6-carboxylic or sulfonic acid,2-chlorobenzo-thiazoleor oxazole-S- or -6- carboxylic or sulfonic acid,1,4-dichloroor 1,4-dibromophthalazine-6-carboxylic acid,2,4-dichloroquinazoline-6- or -7-carboxylic acid,4,5-dichloro-6-pyridazon-l-yl-trimethylene carboxylic acid or-l',4'-pheny1ene carboxylic acid.

Particularly valuable fiber-reactive acyl radicals A are derived from apolyhalide of a cyclic imide of carbonic acid, particularly apolyhalogenopyrimidine and especially from a triortetra-chloropyrimidine.

The starting materials of Formula I are known and can be produced byknown methods, e.g. by coupling the tetrazonium compound from 1 mol of4,4'-diamino-l,1'-diphenyl-3-sulfonic acid on the one hand with 1 mol of2-hydroxynaphthalene-6,S-disulfonic acid and on the other with 1 mol ofan aminobenzene coupling in p-position to the amino group of Formula IIIfr (III) wherein X and Y have the meanings given in Formula I and Rrepresents hydrogen or the methyl sulfonic acid group. Particularlyvaluable as starting material of Formula I is a mixture of two aminodisazo dystuffs which can be produced by using a mixture ofaminobenzenes of Formula III as second coupling component. If desired,the diazonium salt of a 4-amino-4'-acylamino-l,l-diphenyl-3-sulfonicacid, e.g. of 4-amino-4'-acetylamino-l,1- diphenyl-3-sulfonic acid, canalso be coupled with 2-hydroxynaphthalene-6,S-disulfonic acid, theacetylamino group saponified, the amino monoazo dyestuff obtaineddiazotised and coupled with an aminobenzene of Formula III to form theamino disazo dyestuffs of Formula I. If an aminobenzene-N-methylsulfonic acid is used as second coupling component, then the couplingproduct should subsequently be saponified, e.g. by heating the alkalinesolution for several hours at 5060 C.

The halides, particularly chlorides but also anhydrides of thecarboxylic or sulfonic acids mentioned in the discussion of A and,principally, halogen triazines and diazines containing more than onemobile halogen atom, in the latter case particularly triortetra-chloropyrimidine are used as agents introducing the fiber-reactiveradical A.

The reaction of the amino disazo dystuff of Formula I with the acylatingagent as defined is performed in the usual way, advantageously inaqueous medium, optionally SO Na in the presence of inert organicsolvents which can easily be removed such as low aliphatic ketones, e.g.acetone, and preferably in the presence of agents which buffer mineralacid such as sodium or. potassium carbonate, sodium or potassiumhydroxide, dior tri-sodium phosphate or dior tri-potassium phosphate,sodium or potassium acetate or tertiary nitrogen bases such as pyridine.

On completion of the acylation, the obtained fiber-reactive disazodystuff is salted out from its optionally previously neutralisedsolution or suspension with sodium or potassium chloride or isprecipitated with an acid. It is then filtered off under suction, Washedand dried. Advantageously the new fiber-reactive disazo dyestuffs aredried at a moderate temperature, if desired under reduced pressure.

The new fiber-reactive disazo dyestuffs or mixtures of @IJZJ dyestuffsare dark powders which, in the form of their alkali metal salts, havegood water solubility. They are suitable for the dyeing of textilematerial, particularly natural or regenerated cellulose fibers such asstaple rayon, jute, linen, ramie, hemp and, principally cotton, in purescarlet to red shades having good colour strength. Due to theirincreased drawing and fixing power onto cellulose fibers when comparedwith similar reactive disazo dyestuffs, they are suitable in particularfor the dyeing of cellulose material by the exhaustion process from along liquor in the presence of an acid binding agent and a neutral saltwhich accelerates exhaustion such as sodium chloride or sodium sulfate.The goods are introduced into the dyebath at a slightly raisedtemperature, the bath is gradually brought to temperatures of to C. anddyeing is completed at this temperature. The neutral salts whichaccelerate the drawing of the dyestuff can be added to the dyebath, ifdesired, after the actual dyeing temperature has been attained.

The new dyestuffs are chemically bound to the fiber by treatment withacid binding agents. After soaping to remove non-fixed dyestutf, thecellulose dyeings have excellent fastness to washing, water,perspiration, alkali, crocking and light and, in addition, can bedischarged a neutral, pure white. It is surprising that in spite of theincreased drawing power on soaping in baths having a low electrolytecontent, non-fixed dyestuff can be easily and completely washed out.This is an essential condition for good wet-fastness properties ofcellulose dyeings attained with fiber-reactive dyestuffs.

The new fiber-reactive disazo dyestuffs can also be used for the dyeingof fiber material containing polyamide, e.g. of natural polyamide suchas wool or silk, or of synthetic polyamide such as nylon. Naturalpolyamide fibers are dyed in hot, weakly acid, e.g. in acetic acid bathin the presence of auxiliaries which improve the evenness of the dyeingsuch as fatty acid-alkanol-amine polycondensation products, as well as,optionally, in the presence of salts such as sodium chloride or sulfate.Synthetic polyamide fibers are advantageously dyed in a hot acid bath,then rinsed and after-treated in a boiling alkaline bath.

The term lower used in this specification and the appended claimsdefining alkyl or alkoxy radicals, means that such radicals have at most4 carbon atoms.

The following non-limitative examples illustrate the invention further.The temperatures are given therein in degrees centigrade. Percentagesare given by weight unless expressly stated otherwise.

EXAMPLE 1 SO Na 26.4 g. of 4,4-diamino-l,l-diphenyl-3-sulfonic acid arestirred in 300 ml. of water and 40 ml. of concentrated hydrochloric acidand tetrazotised by the dropwise addition of a solution of 13.8 g. ofsodium nitrite in 27 ml. of water. 31 g. of Z-hydroxynaphthalene-6,8-disulfonic acid in the form of the sodium salt are then added to thetetrazo solution and then 25 ml. of concentrated sodium hydroxidesolution are added until the pH of the reaction solution has increasedto 9. As soon as the monoazo dyestufi formation is complete, first 2 ml.of concentrated hydrochloric acid and then 18.7 g. ofaminobenzene-N-methyl sulfonic acid are added.

The deep red solution of the disazo dyestuff formed is heated to 50 42g. of sodium hydroxide are added and the N-methylsulfonic acid group issaponified for 3 hours at 50-60. At the end of this time, the solutionis acidified with 120 ml. of aqueous 30% hydrochloric acid, the aminodisazo dyestuff obtained is salted out by the addition of sodiumchloride and filtered off.

The filter residue is dissolved in 800 ml. of water and 6 g. of sodiumcarbonate at 70 and 17.85 g. of 2,4,6- trichloro'pyrimidine are added.The pH is kept at 6.0-6.5 by the dropwise addition of sodium carbonatesolution. When the condensation at 70" is complete, the disazo dyestuifobtained is precipitated with sodium chloride, filtered off, dried invacuo at 6070 and milled. It is a dark brown powder which dissolves inwater with a scarlet and in concentrated sulfuric acid with a violetcolour. It dyes cotton and regenerated cellulose fibers from a bathcontaining Glaubers salt and sodium carbonate in pure scarlet shadeswhich have good fastness to light, washingand perspiration. The dyeingscan be discharged'a' neutral pure white.

The same dyestuif is obtained by diazotising 4-amino-4'-acetylamino-1,l-dipheny1 3 sulfonic acid, coupling with2-hydroxynaphthalene-6,8-disulfonic acid, saponifying the acetylaminogroup with sodium hydroxide solu tion, diazotising the amino monoazodyestulf obtained and coupling, as described in the example, withaminobenzene-N-rnethyl sulfonic acid saponifying and acylating.

Similar brilliant scarlet dyestuffs are obtained if the amino disazodyestulf described in Example 1 is reacted With the equivalent amount ofone of the acylating agents given in the following Table I, column IIinstead of with 17.85 g. of 2,4,6-trichloro-pyrimidine, the reactionbeing performed at the reaction temperature given in the third column.

TABLE I I II III

Reaction temperature, degrees Shade on cellulose Scarlet.

TABLE I-Continued I II III IV Reaction tempera- Example ture, Shade onNo. Acylating agent degrees cellulose 7 C1 40 Do.

N o1 N 9 N l:c1 10 D0;

Cl-C O N C1 10 S 10 Do:

11 ClOOCH2CH2-Cl 5 Do; 12 CH2=CHCOC]. 0-5 Do.

By repeating each of Examples 1-12, but using, instead of 18.7 g. ofaminobenzene-N-methyl-sulfonic acid, 20.1 g. of2-methyl-l-aminobenzene-N-methyl sulfonic acid for the production of theamino-disazo dyestuff there are obtained similar fiber-reactive disazodyestuifs which afford scarlet dyeings with excellent color yields oncotton.

These dyeings have similar satisfactory fastness properties as those ofExample 1.

EXAMPLE 13 26.4 g. of 4,4-diarnino-1,1'-diphenyl-3-sulfonic acid aretetrazotised as described in Example 1 and coupled with 31 g. of2-hydroxynaphthalene-'6, 8-disulfonic acid. A mixture of 5.3 g. ofS-methyl-l-aminobenzene and 6.05 g. of 2,5'dimethy1-l-aminobenzene isadded to the suspension of the diazoninm monoazo dyestutf obtained, thepH of which is 3. As soon as the coupling is complete, the couplingsolution is made weakly alkaline with 10 ml. of concentrated aqueoussodium hydroxide solution and the amino disazo dyestutf obtained issalted out by the addition of sodium chloride and filtered olf. It isthen. dissolved in 600 ml. of water at then 21.4 g. of2,4,5,6-tetrachloropyrimidine are added to the dyestuif solution and thepH of the solution is kept between 6 and 6.5 by the gradual addition of6.4 g. of sodium carbonate. The condensation is complete after 4 hours.The mixture of dyestuffs of the formulas SO Na on, 01

7 in a molar ratio of about 1:1 is precipitated with sodium chloride,filtered off, washed, dried and milled. It forms a red-brown powderwhich dissolves in water with a scarlet and in concentrated sulfuricacid with a blueand (b) a radical of the formula violet colour. It dyesnatural or regenerated cellulose 5 C fibers from a soda alkaline liquorin deep scarlet shades. I Non-fixed dyestufi can easily be Washed out bysoaping. The dyestuff mixture has less tendency to precipitation I inthe presence of electrolytes than the components. N N

Dyestuffs or mixtures of dyestuffs having similar prop- 10 erties areobtained, if, instead of the mixture of 5.3 g. ofS-methyl-l-aminobenzene and 6.05 g. of 2,5-dimethyll-aminobenzenedescribed in the example, equivalent amounts of one of the other aminesor mixtures of amines Wherem R and R have the meaning as given above;given 1n the followlng Table II, column II, are used and 1 X representshydrogen or a lower alkyl group, and condensation is performed with 21.4g. of 2,4,5,6-tetra- Y m h d o n low r k l 1k chloropyrimidine or one ofthe acylating agents menreprese S y I ge a e a y or a war Oxy tioned inTable I, column II, under the conditions there group described. 2. Adyestuff as defined in claim 1, wherein A repre- TABLE H sentsdichloropyrimidyl or trichloropyrimidyl. 3. A dyestutf as defined inclaim 1, wherein each of X I H m and Y represents hydrogen or methyl.Example Shade on 4. A dyestuff as defined in claim 1, which is of theNo. Amine or mixture 01 amines cellulose formula l4 Mixture 01 3.6 g. of3-methyl-l-aminobenzene Scarlet.

and 8.05 g. of 2,E-dimethyl-l-aminobenzene. 15." 3methyl-1-aminobenzeneDo. i931; 2 32515$$05a35sass::::::::: R31? 011 SOs-W 182-ethoxy-fi-methyl-l-aminobenzene Red; %g gg-gieitshyl-l-aminobenzeneScarlet. N N N=N opropyl-l-aminobenzene.. Do.

Similar dyestuff of satisfactory dyeing properties are obtained whenvarying the molar ratio of 3-methyl-1-aminobenzene to2,5-dimethyl-1-amin0benzene in Example 13 SOTM within the range of from10:1 to 1:10. 1

EXAMPLE 21 NH N 3 g. of the mixture of dyestuffs described in Example N13 are dissolved in a dyebath of 1000 ml. of water and Cl 20 g. ofsodium carbonate are added. 100 g. of mercer- 40 ised cotton areintroduced at 40, the bath is heated to 90 within 30 minutes, 60 g. ofsodium sulfate are added A dyesltuIf a5 defined in Claim 1 Which is ofthe to the dyebath and dyeing is performed for '1 hour at this formulatemperature. The dyeing obtained is then rinsed and soaped at the boilfor 15 minutes.

A deep, scarlet dyeing is obtained which has excellent 0H z-M fastnessto washing, water, perspiration and cracking. I The dyeing can bedischarged a neutral pure white.

I claim: 1. A dyestufi of the formula rM+ 11 S|O,-M+ 1| s'0,

| @mm N SOrM+ X 51 SOrM+ wherem 6O 6. A dyestulf as defined in claim 1which is of the M+ represents hydrogen or an alkali metal ion, for l Arepresents a fiber-reactive grouping selected from '(a) a radical of theformula R SO3"M+ it a Q Q 3 N N SO3 M+ l l b O -M' wherein R representshydrogen, chloro or bromo Q-NH xN R represents chloro or brorno, and N%R represents chloro or bromo; 3 O1 7. A dyestufi as defined in claim 1which is of the References Cited formula UNITED STATES PATENTS 0H3,141,874 7/1964 Ischer et a1. 260154 x f= 5 CHARLES B. PARKER, PrimaryExaminer o C. F. WARREN, Assistant Examiner us. 01. X.R.

CH: 01 C1 10 s- 41 B, so, 51,260-152, 153, 158

